Photosensitive compositions

ABSTRACT

The photosensitive compositions comprising (A) an unsaturated polyester, (B) acrylic acid and (C) a photopolymerization initiator, said unsaturated polyester being produced from an alcoholic component comprising at least one etherdiol having one to four ether-oxygen groups in the main chain and an acidic component comprising at least one unsaturated dicarboxylic acid, anhydride or dimethyl or diethyl ester thereof and having an average molecular weight of 1,500 to 50,000 and a double bond concentration of 1 X 10 2 to 2 X 10 4 mole/g., the amount of (B) acrylic acid being 10 to 80 percent by weight of the total amount of the photosensitive composition and the amount of the photopolymerization initiator being 0.001 to 10 percent by weight of the total amount of the photosensitive composition.

United States Patent Inventors Kiyoshi Akamatsu;

Takeaki Hagihara; Teruhisa Ishldo, all of Tokyo, Japan Appl. No. 772,036

Filed Oct. 30, 1968 Patented Dec. 21, 1971 Assignee Asahi Kasei Kogyo Kabushlki Kalsha Osaka, Japan Priority Nov. 9, 1967 Japan 42/7 I 704 PHOTOSENSITIVE COMPOSITIONS 7 Claims, No Drawings 115 R; 204/l59.l6, 159.19

[56] References Cited UNITED STATES PATENTS 2,79l.504 5/l957 Plambeck 96/! I5 P 3,l36,638 6/l964 Schwerin et al. 204/l59.l5 X

Primary Examiner-William D. Martin Assistant Examiner-D. Cohen Attorney-Burgess, Dinklage 8L Sprung ABSTRACT: The photosensitive compositions comprising (A) an unsaturated polyester, (B) acrylic acidand (C) a photopolymerization initiator, said unsaturated polyester being produced from an alcoholic component comprising at least one etherdiol having one to four ether-oxygen groups in the main chain and an acidic component comprising at least one unsaturated dicarboxylic acid, anhydride or dimethyl or diethyl ester thereof and having an average molecular weight of 1,500 to 50,000 and a double bond concentration of 1X10" to 2X10 mole/g.,'the amount of (B) acrylic acid being l0 to 80 percent by weight of the total amount of the photosensitive composition and the amount of the photopolymerization initiator being 0.00l to 10 percent by weight of the total amount of the photosensitive composition.

1 PHOTOSENSITIVE COMPOSITIONS This invention relates to novel photosensitive compositions photopolymerizable by the action of actinic light and more particularly to photosensitive compositions comprising an unsaturated polyester, at least one addition polymerizable or ring-openable ethylenically unsaturated compound and a photopolymerization initiator.

Photopolymerizable compositions are valuable for manufacturing printing plates, matrices of printing plates, molds for ceramics, casting or molding plastics or reliefs for displays. These articles are easily produced by exposing a layer of photosensitive compositions to actinic light through an imagebearing transparency and then washing off an unexposed areas with a solvent.

It is known that the silver salts in photography and thermoreactive resins in infrared baking and coating utilize the reaction by actinic light in an industrial scale. There are known chrome-containing polyvinylalcohols and polyvinylalcohol cinnamates similar to these compounds in manufactur ing printing plates but they only give a thin photocrosslinked layer of less than 0.1 mm. in thickness and it is impossible to produce thick plates or high relief articles. The articles prepared by photopolymerizing a mixture of a cellulose material and a divinyl compound of a relatively low molecular weight having a terminated unsaturated group suffer from an insufficient hardness, strength and solvent resistance Dicryl (trade name by E. l. Du Pont de Nemours & Co.) has a limited range of hardness and is fragile and deteriorated by humidity, water and especially aqueous alkali solutions. Nyloprint (trade name by Badische Anilin & Soda Fabrik) using soluble nylons has an inferior resistance for alcoholic solvents and weather resistance. These photosensitive compositions are coated in a regular thickness on a metal support and only used in producing printing plates.

The present invention is to provide useful liquid photosensitive compositions applicable to any field which avoid the prior art disadvantages.

The object of this invention is to provide such photosensitive compositions that are soluble in water and aqueous solutions and have a good resolubility and developability, and that are photopolymerized under the influence of actinic light to easily produce photopolymerized articles having precise and clear reliefs and a superior water resistance, solvent resistance, tensile strength, elongation, transparency and any hardness.

According to this invention there have been provided photosensitive compositions comprising (A) an unsaturated polyester, (B) acrylic acid and (C) a photopolymerization initiator, said unsaturated polyester being produced from an alcoholic component comprising at least one etherdiol having one to four ether-oxygen groups in the main chain and an acidic component comprising at least one unsaturated dicarboxylic acid, anhydride or dimethyl or diethyl ester thereof and having an average molecular weight of 1,500 to 50,000 and a double bond concentration of 1X10 to 2X10 mole/g, the amount of (B) acrylic acid being to 80 percent by weight of the total amount of the photosensitive composition and the amount of the photopolymerization initiator being 0.001 to 10 percent by weight of the total amount of the photosensitive composition. In order to increase a resolubility and a developability of the photosensitive compositions, the use of an alcoholic component having a higher molecular weight in producing an unsaturated polyester is insufficient, but it is preferable to increase a concentration of a polar group such as ether, ester or hydroxy group in the unsaturated polyester and the use of an etherdiol having five or more ether-oxygen groups in the main chain as the alcoholic component gives an inferior water resistance and tensile strength to the photopolymerized articles. Also when an alklenediol is used as the alcoholic component, the organic solvent resistance of the photopolymerized articles are inferior. On the other hand, an unsaturated polyester derived from an alcoholic component comprising at least one etherdiol having one to four ether-oxygen groups exhibits an excellent resolubility, developability prior to photopolymerization water resistance and organic solvent resistance after photopolymerization.

The etherdiols utilized for the preparation of an unsaturated polyester are polyoxyethleneglycols of the formula,

H0-(CH2CH2O) r-H wherein n is an iritfirbhpolyoxypropyleneglycols of the formula,

wherein n is 2 to 5, polyoxytrimethyleneglycols of the formula,

wherein n is 2 to 5, polyoxytetramethyleneglycol of the formula,

HO-(CHg-CHz-OHrCHr-O) -11 wherein n is 2 to 5, poly-Z-methyloxybutandiol of the formula,

glycerin-propyl etherdiol monoacetate, glycerinpropylethertriol monolaurate, trimethylolpropane-propylethertriol monopropionate and trimethylolpropane-propylethertriol monooleate.

Examples of suitable polyols which may be used for modifying the unsaturated polyesters are ethyleneglycol, propyleneglycol, neopentylglycol, trimethyleneglycol, tetramethyleneglycol, pentamethyleneglycol, hex

amethyleneglycol, glycerine monooleate, trimethylolpropane monooleate, glycerol, trimethylolpropane, erythritol, pentaerythriotol, pentitol, bis-(hydroxyethyl)terephthalate, bis- (hydroxyethyl)phthalate, bis-(hydroxypropyl)terephthalate.

Exemplary unsaturated dicarboxylic acids, anhydrides, and dimethyl or diethyl esters thereof utilized for the preparation of an unsaturated polyester include maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, chloromaleic acid,

citraconic acid, citraconic anhydride, methaconic acid,

itaconic acid, muconic acid, glutaconic acid and aconitic acid.

Inorder to improve the tensile strength, hardness, solvent resistance, abrasion resistance, impact resistance and flexibility of the photopolymerized articles, a part of the unsaturated dicarboxylic acids, anhydrides or methyl or ethyl esters may be substituted with a carboxylic acid, anhydrides or methyl or ethyl esters thereof to vary a double bond concentration in an unsaturated polyester. The term double bond concentration means the mole concentration of double bond per 1 g. of an unsaturated polyester. The double bond concentration is preferably in the range of IX 10' to 2X10 mole/g. When the double bond concentration is above 1X10 mole/g. the hardness becomes so great that the photopolymerized articles exhibit substantially neither flexibility nor impact resistance. On the other hand when the double bond concentration is below 2X10" mole/g, the photopolymerization only proceeds to such an extent as to give a photopolymerized article having a poor resolubility and solvent resistance, which is of no use for practical purposes.

Such carboxylic acids, anhydrides and methyl or ethyl esters thereof which can be used for modifying an unsaturated polyester, include succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, dimethylesters, diethylesters thereof, phthalic anhydride, palmitic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

(A) An unsaturated polyester, i.e., the first component of the present photosensitive compositions can be produced by a conventional process. Usually an unsaturated polyester is formed by direct esterification, ester exchange or addition reaction between (a) an etherdiol, if desired, modifying agent such as polyols and (b) an unsaturated dicarboxylic acid and/or its anhydride and/or its dirnethyl or diethyl ester, if desired, modifying agents such as carboxylic acids, anhydrides or methyl or ethyl esters thereof.

It is preferred to use the unsaturated polyesters having an average molecular weight of from 1,500 to 50,000. When the average molecular weight of the unsaturated polyesters is below 1,500, the flexibility after photopolymerization is not sufficient. On the other hand the preparation of unsaturated polyesters having an average molecular weight above 50,000 becomes difficult and a developability of the photosensitive compositions comprising such unsaturated polyesters is extremely poor, not giving clear and precise patterns.

As the second component of the present photosensitive composition, the most preferable addition polymerizable ethylenically unsaturated compound is (El acrylic acid. Firstly, acrylic acid improves remarkably the rate of photopolyrnerization and secondly, may give the desired hardness to the photosensitive composition after photopolymerization by varying the amount of acrylic acid. Thirdly, acrylic acid gives a superior resolubility to the photosensitive compositions and fourthly, improves greatly the tensile strength of the photosensitive compositions after photopolymerization. Fifthly, owing for its affinity to water, acrylic acid improves the dispersibility of the unsaturated polyesters in water which makes it possible to develop the photosensitive compositions with an aqueous solution and sixthly, gives a good transparency to the photosensitive compositions after polymerization owing to its affinity for the unsaturated polyesters.

It is preferred to employ acrylic acid in amounts of from 10 to 80 percent by weight based upon the total amount of the photosensitive composition. When the amount of acrylic acid is less than l percent by weight, the rate ofphotopolymerization is very slow and the mechanical strength after photopolymerization is too low for practical use. When said amount is more than 80 percent by weight, the photopolymcrization does not fully proceed so as to exhibit the characteristics of the unsaturated polyesters as a frame for photopolymerization and the organic solvent resistance as well as the resolubility are unfavorably lowered.

It has been found that when (D) a compound of the formulas;

wherein R,, R and R, represent hydrogen atom or methyl group; R represents hydrogen atom,C,,,H,,,, wherein m is an integer from I to 6, cyclohexyl,(CH,),,0l-l wherein n is an integer from 1 to 5, (CH CH whereinp is an integer of from I to 2 and q is O or an integer from l to 5 orCH CH=CH R. represents(CH ),wherein r is an integer from 1 to 10, is used together with acrylic acid, the tensile strength after photopolymerization may be markedly improved while maintaining the rate of photopolymerization of acrylic acid, and that the compounds as such has no compati bility with the unsaturated polyester.

Such compounds include, for example, acrylumidc. mcthacrylamide, N,N-dimcthylucrylamidc, N-- isopropylacrylnmidc. N-hcxylucrylumide, N-cyclohexylucrylumide, N-mcthylolucrylumidc, N-ethylolucrylumidc, N- amylolacrylamide, N-allylacrylamide, N,N'-methylene bisacrylamide, N,N'-trimethylene bisacrylamide, N,N--hexamethylenebisacrylamide, N,N'-decamethylenebisacrylamide, N-methoxyethylacrylamide, N-methylmethacrylamide, N-allylmethacrylamide, N-methylolmethacrylamide, N,N- methylenebismethacrylamide and N'ethoxyethylmethacrylamide. Among these compounds acrylamide is most preferable for showing the above-mentioned effect. At most 75 percent by weight of acrylic acid may be preferably substituted by said compound. When the amount of said compound is more than 75 percent by weight, the compatibility with the unsaturated polyesters and acrylic acid is lost and the photopolymerization is hindered to greatly lower the tensile strength after photopolymcrization.

It has also been found that when (Ell a compound having at least one group and one benzene nucleus is used together with acrylic acid, the transparency and water resistance are remarkably increased.

Such compounds include, for example, styrene, divinylbenzene, alpha--methylstyrene, vinyltoluene, alphachlorostyrenc, vinylchlorobenzene, vinylphenol, aminostyrene, vinylbcnzoic acid, methoxystyrcne, allylwherein R and R represent hydrogen atom, chlorine atom or methyl; R represents hydrogen atom, --C,,.H,,, ,wherein m is an integer from i to l5,

wherein n is an integer from I to 2 andp is an integer from I to 5.

or (CH,Cl-l,-O),,-H, wherein q is an integer from 1 to and R represents -(CH,-CH,0),-wherein r is an integer from 1 to 15, is used together with acrylic acid,.the elongation after photopolymerization is increased and consequently an excellent flexibility is afforded.

Such compounds include, for example, methylacrylate, ethylacrylate, methylalphachloroacrylate, butylacrylate, isobutylacrylate, propylacrylate, lethylhexylacrylate, n-octylacrylate, n-decylacrylate, n-tetradecylacrylate, allylacrylate, furfurylacrylate, glycidylacrylate, methacrylic acid, methylmethacrylate, butylmethacrylate, isobutylmethacrylate, 2-ethylhexylmethacrylate, laurylmethacrylate, furfurylmethacrylate, diethyleneglycol diacrylate, tetraethyleneglycol diacrylate, ethyleneglycolmonomethacrylate diethyleneglycolmonoacrylate, hexamethyleneglycoldimethacrylate, tetradecylethyleneglycoldimethacrylate, 2- hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2- hydroxyhexylmethacrylate and glycidylmethacrylate. Among these compounds methylacrylate and butylacrylate are most preferable. At most 90 percent by weight of acrylic acid may be preferably substituted by said compound. When the amount of said compound is more than 90 percent by weight, rate of photopolymerization is extremely retarded and a tensile strength after photopolymerization is lowered.

Still more to improve the properties of the photosensitive compositions before and after photopolymerization, two or three of said compounds (D), (E) and (F) may be used together with (B) acrylic acid at the same time. it is preferred to employ the third compound (E) or (F) in amounts of at most 80 percent by weight of the total amount of (B) acrylic acid and said compound (D) or (E) and to employ the fourth compound (F) in amounts of at most 70 percent by weight of the total amount of (B) acrylic acid and said compounds (D) and (E) for the exhibition of the aforementioned characteristics of said third or fourth compound to be added.

The unsaturated polyesters according to the present invention can be photopolymerized with the aforesaid ethylenically unsaturated compound with the use of a known photopolymerization initiator.

Examples of suitable such photopolymerization initiator include benzoins such as benzoin, alpha-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, alphaphenylbenzoin, alpha-allylbenzoin; anthraquinones such as anthraquinone, chloroanthraquinone, methylanthraquinone, tert-butylanthraquinone; peroxides such as benzoyl peroxide, methylethylketone peroxide, potassium persulfate, disulfide such as diphenyl disulfide, tetraethylthiuram disulfide, diketones such as benzil, diacetyl; uranyl salts such as uranyl nitrate, uranyl propionate; Z-naphthalene sulfonyl chloride; metal halides such as silver chloride, silver bromide, stannic chloride, stannous chloride and titanium chloride.

These photopolymerization initiators are preferably used in proportion of 0.001 to l0 percent by weight based upon the total amount of the photosensitive composition. When the amount of the photopolymerization initiator is less than 0.00l percent by weight, the photopolymerization reaction is greatly retarded and is disadvantageous from the practical point. On the other hand when said amount is more than l0 percent by weight, the photosensitization is not fully intensified for its amount and is disadvantageous from the economical point.

Known stabilizers may be employed for the purpose of maintaining a storage stability and a better resolubility of the photosensitive compositions. Such stabilizers may be added when the components of a photosensitive composition are admixed or may be preliminarily added to each component prior to admixing the components.

Exemplary such stabilizers include hydroquinone, monotert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, catechol, p-tert-butyl catechol, benzoquinone, 2,5-diphenylp-benzoquinone, pyridine, phenothiazine, p-diaminobenzene, beta-naphthol, naphthylamine, pyrogallol, cuprous chloride and nitrobenzene. These stabilizers are added only for completely preventing the dark reaction without restraining the photopolymerization reaction. Consequently the amount of the stabilizers is preferably varied from 0.005 to 3.0 percent by weight of the total amount of the photosensitive composition.

The present photosensitive compositions are readily photopolymerized by actinic light having wave lengths below 7,000 Angstroms, generally between 2,000 and 5,000 Angstroms. Practical sources of such actinic light include carbon arc lamps, super high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, UV fluorescent lamps, xenon lamps and sunlight.

When the photosensitive compositions are exposed to actinic light at a distance of from about 5 cm. to about l00 cm through, for example, a photographic negative film, the image areas of the compositions are substantially photopolymerized in about I to 30 minutes to be rendered completely insoluble. The nonimage areas of the compositions may be washed out with water or an aqueous solution. Exemplary aqueous solutions include aqueous solutions of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate; mixture solutions of water with water soluble organic solvents such as methanol, ethanol, isopropanol, acetone, dioxane, tetrahydrofuran and phenol; and aqueous solutions of various kinds of surfactants.

The photosensitive compositions according to the present invention are especially useful for manufacturing various printing plates such as letterpress printing plates, gravure printing plates, high-etched offset printing plates, deep-etched printing plates, planography printing plates, name plates, memorial stamps, silk screens, screens for textile printing and process screens. Further, the photosensitive compositions are useful for manufacturing matrices of printing plates, molds for ceramics and molds for casting or molding plastics; and reliefs for display and indication applications, patterns and braille points.

This invention will be illustrated by the following examples which are in no way limiting upon the scope hereof. Parts are by weight unless expressly stated to the contrary.

EXAMPLE I Under an atmosphere of nitrogen gas, 0.25 mole of polyoxyethylene glycol having an average molecular weight of 200, 0.25 mole of dioxyethylene glycol, 0.23 mole of maleic acid and 0.27 mole of adipic acid were reacted at 180 C. for 6 hours to produce an unsaturated polyester having an average molecular weight of 10,000 and a double bond concentration of 1X10 mole/g. To 100 parts of the unsaturated polyester thus obtained, there were added 0.1 part of hydroquinone, 60 parts of acrylic acid, 40 parts of styrene and 1 part of benzoin methylether and these were thoroughly mixed to produce a photosensitive composition.

To a glass cell consisting of a spacer of 10 mm. in height forming four sides of the cell, a bottom plate of a transparent glass, and a top plate of a transparent glass on which a negative film carrying a transparent image of a double eagle was tightly fixed, the aforesaid photosensitive composition was placed. The negative film side of the cell was exposed for 10 minutes to the light from a 3 kw. carbon arc lamp at a distance of cm. The unexposed areas were removed by washing with a 20 percent aqueous acetone solution to give a plastic pattern of l0 mm. in thickness precisely and clearly corresponding to the image of the negative.

EXAMPLE 2 A variety of unsaturated polyesters shown in table I were prepared in the same manner as in example 1. To parts of the unsaturated polyester, there were added 40 parts of acrylic acid, 2 parts of benzoin and 0.1 part of tert-butylcatechol and these were thoroughly mixed to produce a photosensitive composition. Each resulting photosensitive composition was exposed for 20 minutes to 60 w. fluorescent lamps for duplicate at a distance of 5 cm. and then a tensile strength, an

elongation, a water absorption were measured. Also a water dispersibility of the photosensitive composition before photopolymerization was measured. The results are shown in table l.

TABLE 1 Double bond concentrntion Average Tensile Water Water Example Unsaturated dicarboxylic (mole/ molecular strength 1 Elon nbsorpdispers- Number Etherdiol (mole) acid (mole) gram) weight (kg/cm!) gation tion 3 ibllity 2 Ethyleneglycol, 0.60 Maie1canhydrlde,0.25. 3) 10- 2,200 140 B 2.0 Separasebaclc acid, 0.26. ted. 3 Trioxyethyleueglycol 0.50 .do 2)(10- 7, 120 (1 2. 3 Good. 4 Polyoiryethyleneglycol (average molecular ....do 2 10 9,500 125 C 3.1 Do.

weight: 200), 0.50. 5 Polyoxyethyleneglycol (average molecular ....d0 5X10 16,200 30 ii as Do.

weight: 1,000), 0.60. 6 Polyoxyethyleneglycol (average molecular .....d0 2X10 20,000 30 I1 103 Do.

weight: 2,000), 0.60. Propyleneglycol, 0.50 Maleic acid, 0.26; adlplc 1i) l0- 2, 700 145 C 1, 2 Separaacid, 0.25. ted. 8 Trloxypropyleneglyeol,0.60 "do. 2X10 5,400 146 C 1.0 (100d.

Polyoxypropyleneglycol (average molecular do... 2)(10- 5,000 136 C 2.3 Do.

weight: 200), 0.50. 10 Polyoxypropyleneglycol (average molecular do b 10- 13, 000 66 ll 33. 2 D0.

weight: 1,000), 0.50. 11 Polyoxypropyleneglycol (average molecular Malelc acid, 0.26; adipic 2X10" 17,000 60 B 37. 2 Do. 1 f i i' 'z i 1 1 1 M 1 1 1 5 2 Et y ene lyco 0. 5; tr oxypropy ene yco. 1 ae cac 0.25 f Phthalic anhydride0.'25...} a L 13 Dlogyethyleneglycol, dioxypropyleneglycol, ..d0 2 10-= 5, 700 140 C 2. 1 D0.

Noam-Conditions oi measurement:

1 Tensile stren th: ASTM D638-68T. 2 Elongation: STM D638-58T; A=0-60%, B =50-100%, C =100-200%, 1) Zoo-300%. E 300%. 3 Water absorption: ASTM D670-57T. 4 Water dispersibility: After stirring tor 10 minutes a 10% aqueous mixture solution of the photosensitive tomposltlons by n homomlxcr.

EXAMPLES 14 to 38 0.25 mole of dioxypropylene glycol, 0.25 mole of polyoxyethylene having an average molecular weight of 200. 0.23 mole of fumaric acid and 0.27 mole of adipic acid were polycondensed in the same manner as in example l to obtain an unsaturated polyester having an average molecular weight of 9,000 and a double bond concentration of 1X10 mole/g. To 100 parts of the unsaturated polyester thus obtained a desired amount of a variety of ethylenically unsaturated compounds shown in table II and 2 parts of benzoin were added and these were thoroughly mixed to give photosensitive compositions. Each resulting photosensitive compositions was exposed for 20 minutes to w. fluorescent lamps at a distance of 10 cm. and then a tensile strength, a transparency, a water dispersibility and a gell up time were measured. The results are shown in table ll.

TABLE II Tensile Water (loll Example Ethylenlcally unsaturated (Parts by strength 1 disperalup number compound weight) (kgjcmfl) Transparency 1 bility 3 time i 25 A 60 A A 200 A 300 A 100 Ii Butylacrylate........ 100 B 21. Trloxyethyleneglycoldiacryla 100 ll 22. Methyl methacrylate 22 2 100 (l 23.. Acrylamide 60 24. N,N'-methylenc-blsacrylate. 50 26.. Styrene 100 B 26 Dlallyl hthalate 100 ii Vlnylto uene 100 li inyl benzolc acid. 100 23 1i Vinyl acetate 100 7 Translucent.. 1) Vinyl chloroacetatc 100 4 Translucent. l) Acrylonitrlle 100 12 Opaque. I -vlnylpyridlnc 100 2 Dlscolora l) Methyivinyl ketonn 100 6 Translucent Good. l) Methylvlnyl ether 100 4 .do Separated. 1) Aliyl alcohol 100 5 do Good.... Methylmaleate 100 30 Opaque... Separated. C N-vlnylpyrolidone 100 4 Discolored. Good. I) l-hexene 100 NoTE.-Conditions of measurements:

Tensile strength: The same as in Examples 2-13.

3 Transparency: Judged with the unaided eye.

1 Water dlspersibility: The same as in Examples 2-13.

4 (iell up time: Time for the photopolymerlzation of the photosensitive composition 015 mm, in ihlckncss. A=0-5 minutes, B =5-60 minutes, C=50100 minutes, 1') 100 minutes.

5 Incompatible.

" Not photopolymerized.

9 3,628,963 EXAMPLES 39m 63 0.250 mole of ethylene glycol, 0.250 mole of diethylene glycol, 0.028 mole of glutaconic acid and 0.472 mole of succinic acid were polycondensed in the same manner as in example l to produce an unsaturated polyester having an average 5 molecular weight of 7,000 and a double bond concentration of 3X10 mole/g. To 100 parts of the unsaturated polyester thus obtained, there were added a desired amount of acrylic acid, a desired amount of a variety of ethylenically unsaturated compounds shown in table ill and 2 parts of benzoin to produce photosensitive compositions. Each resulting photosensitive composition was exposed for 20 minutes to 60 w. fluorescent lamps at a distance of 5 cm. and then a tensile strength, an elongation, a transparency and a gell up time were measured.

The results are shown in table Ill.

TABLE III (Parts Tensile 0011 Example Ethylenically unsaturated by strength Elongaup Number compound weight) (kg/cm!) tion Transparency= time 4 39 1. Acrylic acid 00 0 Transparent.... A 40 d0 38 115 0 do A 150 (l A d d (lg 256 I;

cry caci 2 43 "{N,N-methylene- 1s-acrylamide. 13 195 B Translucom-m- A 44 300 11 do A 16 45 430 11 A III: 120 0 Transparent. A 25 25 140 L A 110 C ..do ii 2 1 13 120 E do..-. A 5? 120 E Translucent... A

64 110 1) d0 B E2 166 1) do 1; Acrylic acid 25 53 zx-hytfi'oxyipdropylm 125 D B cry cac 54 2A-ethfilhexyalacrylate no D A cry caci 55 '{Xinyhacetage 35 A C cry caci 56 "{iLvulyylpyllgflidonm 5g 15 A Discolored .s 1) cry ic ac t 57 i 3g 40 B Opaque L Acry eaci 58 A fi, l 2g 45 A Translucent C cry cac iithyllivinyli ether 15 A 1) cry caci t 60 lA/[ethlyl maeate... Q A

cry 10 aci 61 "{illyllfilcohgl A C cry caci s2 vmfilpyrligmmn I 20 A Discolorcd 1) cry eac e3 25 15 A Opaque l) NOTE.C01ld1t101'lS of measurements:

1 Tensile strength: The same as in Examples 2-13. 9 Elongation: The same as in Examples 2-13.

I Transparency: The same as in Examples 14-38. 1 Gail up time: The same as in Examples 14-38.

EXAMPLES 64-72 60 0.25 mole of polyoxytetramethylene glycol having an average molecular weight of 300, 0.25 mole of bishydroxyethylphthalate, 0.09 mole of maleic acid and 0.41 mole of succinic acid were polycondensed in the same manner as in example i to produce an unsaturated polyester having an average molecular weight of 10,000 and a double bond concentration of 5X10" moi/g. To 100 parts of the unsaturated polyester thus obtained, there were added a desired amount of acrylic acid, a desired amount of a variety of ethylenically un- 70 saturated compounds shown in table IV and 2 parts of benzoin to produce photosensitive compositions. Each resulting composition was exposed for 20 minutes to 60 fluorescent lamps at a distance of 10 cm. and then a tensile strength, an elongation,

a transparency and a water absorption were measured. The results are shown in table IV.

TABLE IV 'iihl Example Ethylenically (Parts by Tensile Elon mnl\sorp N umber unsaturated compound weight) strength tion 'Irmispurmn'y lion (kg/cm!) Acrylic acid 25 64 Acrylamide 25 350 Transparvntun 0.6

Styrene 25 Acrylic acid 2O 65 Acrylamide 20} 345 0.3

Diallylphthalatc. 4O Acrylic aci 10 66 Acrylamide 10 200 .do. i. 2

Monoallyl hthalatc... (i Acrylic ac d 25 l 67.. N-methylolacrylamide 25 350 I) 'lrrmslm'cnlv 2. I

Ethylacrylate 25 l Acrylic acid 20 68.. N-methylolacrylamidc 20 325 i; do I.

Butylacrylate 40 Acrylic acid 69 N-methylolacrylamido 10 315 l) .rlo.. 5

Pentlacrylate (l0 Acrylic acid" 25 70 Methacrylamld 25 70 ll Opaque. 7

Vinylacetate. 25 Acrylic acld-. 25 71 Methacrylamlde 26 05 it do..

Acrylonitrile Acrylic acid 25 72 Methacrylamflde 25 5 A 'lrmrslucvnL. 2

Ethylvinyl ketone 25 N01E.Condltions of measurements:

1 Tensile strength: the same as in Examples 213. 1 Elongation: the same as in Examples 2-13. 1 Transparency: the same as in Example 14-38. 4 Water absorption: the same as in Example 14-38.

EXAMPLES 73-78 0.25 mole of trimethylolpropane monooleate, 0.25 mole of polyoxypropyleneglycol having an average molecular weight of 300, 0.1 1 mole of maleic anhydride and 0.39 mole of adipic acid were polycondensed in the same manner as in example i to produce an unsaturated polyester having an average molecular weight of 13,000 and a double bond concentration of 5X10 mole/g. To 100 parts of the unsaturated polyester thus obtained, there were added a desired amount of acrylic acid, a desired amount of a variety of ethylcnically unsaturated compounds shown in table V and 2 parts of benzoin to produce photosensitive compositions. Each resulting photosensitive composition was exposed for 10 minutes to a 3 kw. carbon arc lamp at a distance of 80 cm. and then a tensile strength, an elongation and a transparency were measured. 45 The results are shown in table V.

TABLE V (Parts Tensile Example Ethylenically by strength 1 E1011- Number unsaturated compound weight) (kg/cm!) gation 2 Transparency 3 Acrylic acid 25 73 Styrene 25 240 D Transparency.

Methylmethacrylate 25 Acrylic acid 20 74 tyrene 20 225 E Do.

Methyiacrylate 40 n? 133-1-- 3 D a y p a ate 1 75 Dioxyethyleneglycol 215 D monoacrylate. Acrylic acid.. 25 76 25 45 A Do.

25 Acrylic acid.. 25 77 Diallylphthal 25 B Do.

Methylvinyl ketone. 25 Acrylic acid 25 78 Styrene 25 40 A Discolored.

4-vinylpyridine 25 NOTE.C0nditions of measurements:

1 Tensile strength: the same as in Examples 2-13. 2 Elongation: the same as in Examples 2-43. W 3 Transparency: the same as in Examples 14-38.

EXAMPLES 79-86 0.250 mole of propyleneglycol, 0.250 mole of polytetramethylene glycol having an average molecular weight of 300, 0.068 mole of itaconic acid and 0.432 mole of succinic acid were polycondensed in the same manner as in example 1 to produce an unsaturated polyester having an average molecular weight of 9,000 and a double bond concentration of 5X10" mole/g. To 100 parts of the unsaturated polyester thus obtained, there were added a desired amount of acrylic acid and acrylamide, a desired amount of a variety oi" unsaturated compounds shown in table VI and 2 parts of benzoin to produce photosensitive compositions. Each resulting photosensitive composition was exposed for l minutes to a 3 kw. carbon arc lamp at a distance of 80 cm. and then a tensile strength, an elongation and a transparency were measured. The results are shown in table VI.

tightly fixed. The transparent glass side of the cell was firstly exposed for 2 minutes and secondly the negative side was exposed for 5 minutes to 60 w. fluorescent lamps for duplicate at a distance of i0 cm. The unexposed areas were removed by washing with a 5 percent aqueous ammonia solution to give a flexible hali'tone block of L5 mm. in total thickness consisting of a relief portion of 0.5 mm. in height and a photopolymerized supporting substrate layer oi l mm. in height. The four color work was run by using the hali'tone block to give clear four color prints having a good dimensional stability.

TABLE VI (Parts Tensile Example Ethylenically by strength 1 Elon- N umber unsaturated compound weight) (kgJcmJ) gatlon I Transparency 3 Acrylic acld 17 79 ggggg qf' 330 E 'lranspalent.

Methylecrylatc 26 Acrylic acid 0 f r fifff; ll E Methylacrylate 60 Acrylic acid. 17 H1 f r fifilfiit i3 1) Methyl mcthaerylatc.. 26 Acrylic acid 17 Aer lamide 17 82. Dla ylphthalate 17 340 1) D0.

2-hydroxypropylmethaerylatc. geryyc aicdid. i7 cry am e. 7 83 17 300 E De.

Butylacrylate. 26 fieryPc aiclid" i7 cry am e 7 84 Diallylphthalate 17 D G1ycidylmethacrylate 26 fi yl a cry am e. I 85 styrene 17 90 B De.

Vinyl acetate 25 2"? til i;

cry am e- 86 Diallly1phthalate 17 110 B Acry onltrlle 25 NorE.Conditions of measurements:

l Tensile strength: the same as in Examples 2-13. 1 Elongation: the same as in Examples 2-13. 3 Transparency: the same as in Examples 14-38. u

EXAMPLE 87 To 70 parts of the unsaturated polyester in example l4, there were added 10 parts of acrylic acid, l0 parts of acrylamide, 10 parts of styrene and 0.] part of anthraquinone and these were thoroughly mixed to give a photosensitive composition. To a glass cell consisting of a spacer of 1.5 mm. in height forming four sides of the cell, a bottom plate of a transparent glass and a top plate of a transparent glass on which a facsimile negative for newspaper was tightly fixed, there was placed the aforesaid photosensitivecomposition. The negative side of the cell was firstly exposed for 5 minutes and secondly the transparent glass was exposed for 2 minutes to 60 w. fluorescent lamps for duplicate at a distance of i0 cm. Then the unexposed areas were removed by washing with a 0.3 percent aqueous sodium hydroxide solution to give a printing plate for newspaper having a sufficient flexibility and toughness. The printing plate thus obtained was fixed on the saddle of a rotary press and a rotary printing was run to give about 400,000 prints.

EXAMPLE 88 To 60 parts of the unsaturated polyester obtained in example 39, 10 parts of acrylic acid, 10 parts of styrene, l0 parts of butylacrylate and l part of benzoin methylether were added and these were thoroughly mixed to obtain a photosensitive composition. The resulting photosensitive composition was placed to a glass cell consisting of a rubber spacer of 1.5 mm. in height forming four sides of the cell, a bottom plate of a transparent glass and a top plate of a transparent glass on which a color separation negative of l75 lines per inch was EXAMPLE 89 To 100 parts of the unsaturated polyester obtained in example i4, 40 parts of acrylic acid, 20 parts of styrene, 40 parts of methylacrylate, 4 parts of diphenyl disulfide and 0.2 parts of hydroquinone were added and these were thoroughly mixed to obtain a photosensitive composition. The resulting photosensitive composition was placed on a tin plate gained with sands of 300 mesh which four sides were surrounded with a spacer of 0.2 mm. in height. On the spacer a polyester film of 0.009 mm. in thickness was placed and a negative was tightly fixed on the polyester film. Then the negative side was exposed for 5 minutes to 60 w. fluorescent lamps at a distance of 5 cm. The unexposed areas were removed by washing with a 20 percent aqueous methanol solution to give a dry-offset printing plate. The resulting printing plate exhibited a sufficient printing resistance and a superior ink transference through a rotary printing.

EXAMPLE 90 To I00 parts of the unsaturated polyester obtained in example 73, 20 parts of acrylic acid, 20 parts of aerylamide, l0 parts of diallylphthalate, 10 parts of methyl methacrylate and 0.5 parts of benzophenone were added and these were thoroughly mixed to obtain a photosensitive composition. The resulting photosensitive composition was placed on a glass plate which four sides were surrounded with a rubber spacer of 2 mm. in height. On the spacer a transparent glass on which a polyester film carrying an image of a cartoon for POP advertisement was tightly fixed, was placed. The negative film side was exposed for 10 minutes to the light from a 3 kw. carbon are lamp at a distance of 75 cm.

The unexposed areas were removed by washing with a 0.1 percent aqueous potassium hydroxide solution to give a cartoon article for POP advertisement of 2 mm. in thickness adhered to a glass plate. This article was dyed in a 2 percent Malachite Green (C.l. Basic Green Vi: 42,000) dyeing bath for l0 minutes to give a beautiful glass display.

What is claimed is:

l. A photosensitive composition comprising (A) an unsaturated polyester, (B) a mixture of ethylenically unsaturated compounds (C) a photopolymerization initiator, said unsaturated polyester being produced from an alcoholic component comprising at least one diol having one to four ether-oxygen groups in the main chain and an acidic component comprising at least one unsaturated dicarboxylic acid, its anhydride or its methyl or ethyl ester and having an average molecular weight of 1,500 to 50,000 and a double bond concentration of 1X10 2 to 2X10" mole/g, said mixture (B) constituting l0 to 80 percent by weight of the photosensitive composition and the photopolymerization initiator constituting 0.001 to percent by weight of the photosensitive composition, said mixture (B) comprising (i) at least 10 percent by weight of acrylic acid, (ii) up to 75 percent by weight of an amide of the formula wherein R,, R and R represent a hydrogen atom or methyl group; R represents a hydrogen atom, -C,,,H,,,, wherein m is an integer from 1 to 6, a cyclohexyl group, -(CH,),,OH wherein n is an integer from 1 to 5, (CH,),0-(C1H,),, Cll'i wherein p is an integer from 1 to 2 and q is 0 or an integer from I to 5 or a CH CH= CH group; R, represents (CH ),-wherein r is an integer from 1 to 10, (iii) up to 90 percent by weight of an aromatic vinyl compound having at least one group and one benzene nucleus in the molecule, and (iv) up to 90 percent by weight ofa compound of the formula /lia (7H1 (l wherein R and R represent a hydrogen atom, a chlorine atom or methyl group; R-, represents a hydrogen atom, C,,, H

wherein m is an integer from 1 to 15 wherein p is an integer from 1 to 2 and m is an integer from I to 5,

or (CH,-CH -0),,H wherein q is an integer from l to 15; and R, represents (ClH -CH,-0),wherein r is an integer from 1 to l5.

2. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains acrylamide.

3. A photosensitive composition as claimed wherein the mixture (B) contains styrene.

4. A photosensitive composition as claimed wherein the mixture (B) contains diallylphthalate.

S. A photosensitive composition as claimed wherein the mixture (B) contains methylacrylate.

6. A photosensitive composition as claimed wherein the mixture (B) contains butylacrylate.

7. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains styrene or diallylphthalate, and methyl or butylacrylatev in claim 1 in claim 1 in claim I in claim I P0405 -UNITED STATES PA'I'ENT OFFICE I. r 'W I Y CERTIFICA FL OF ORREQ HON Patent No. 3,628,963 Dated December 21, 1971 lnventofls) Kiyoshi Akazhatsu et al. I

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

"an" should be --the C01. 1 line 14 H II Col. 1, line 57 delete last "-(CH -CH should be --(CH -O-(CH (311 col. 3', line 68 Signed and sealed this 6th de or; June 1972.

(SEAL) Attest: v

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner'- of Patents 

2. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains acrylamide.
 3. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains styrene.
 4. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains diallylphthalate.
 5. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains methylacrylate.
 6. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains butylacrylate.
 7. A photosensitive composition as claimed in claim 1 wherein the mixture (B) contains styrene or diallylphthalate, and methyl or butylacrylate. 